Adsorbent composites for sorption cooling process and apparatus

ABSTRACT

A desiccant cooling apparatus and process using a solid adsorbent and refrigerant wherein the solid adsorbent is selected from the group consisting of zeolite Y-85, a low cerium rare earth exchanged Y-84 and a rare earth exchanged LZ-210, and the adsorbent is bonded directly to the heat exchange tubes within the device by a novel slip coating process resulted in significant improvements in thermal efficiency and overall performance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of copending application Ser. No. 08/124,740, filed on Sep. 21, 1993, and issued on Oct. 10, 1995 as U.S. Pat. No. 5,456,093, which is a continuation-in-part of Ser. No. 07/895,975, filed Jun. 9, 1992, and issued on Nov. 9, 1993 as U.S. Pat. No. 5,260,243, which is a continuation-in-part of Ser. No. 07/386,319, filed Jul. 28, 1989, and issued on Jun. 9, 1992 as U.S. Pat. No. 5,120,694 and the above herein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates in general to adsorbent composites and more particularly to methods for coating the inside surface of a tube with a layer of solid adsorbent to form an adsorbent-lined tube, to a process for sorption cooling utilizing the adsorbent-lined tube and to an apparatus useful for sorption cooling.

BACKGROUND OF THE INVENTION

There are a variety of solid adsorbents which have been useful in adsorption and catalysis including commonly known materials such as activated carbons, activated clays, silica gel, activated alumina, and crystalline molecular sieves. Of these adsorbents, crystalline molecular sieves such as silicoalumino phosphates, aluminophosphates and aluminosilicate zeolites have been particularly useful because of their uniformpore size.

In many instances it is desirable to have the solid adsorbent deposited on a substrate as a coating instead of being contained in particulate form as pellets, beads, or other particles. There are several reasons why solid adsorbent coatings have been used including for example, to improve the catalytic or adsorption properties of the solid adsorbent by improving the surface area to weight ratio, to reduce the mount of solid adsorbent required, to protect the underlying substrate material from a harmful environment, to achieve a particular strength or form, and, to perform the particular adsorptive or catalytic function over the entire coated surface of the substrate.

Despite the diversity of coating methods and end uses known to exist, new methods are sought which can be used to coat the inside surfaces of tubes with solid adsorbents without the use of adsorbent formation reactions, frits and enamels, paints, varnishes and the like, in order to provide adsorbent-substrate composites that have physical and performance properties suitable for sorption cooling use.

Some thermodynamic processes for cooling and heating by adsorption of a refrigerating fluid on a solid adsorbent use zeolite, and other sorption materials such as activated carbon and silica gel. In these processes, the thermal energy from adsorbing zeolite in one place is used to heat desorbing zeolite located in another place. U.S. Pat. No. 4,138,850 relates to a system for such solar heat utilization employing a solid zeolite adsorbent mixed with a binder, pressed, and sintered into divider panels and hermetically sealed in containers. U.S. Pat. No. 4,637,218 relates to systems for a heat pump using zeolite as an adsorbent wherein the zeolite is prepared by slicing natural zeolite rock with a carbide saw, or by pressing slightly-wetted, powdered zeolite into bricks. The bricks used in U.S. Pat. No. 4,637,218 are preferably not more than 10 mm in thickness.

U.S. Pat. No. 4,548,046 relates to an apparatus for cooling or heating by adsorption of a refrigerating fluid on a solid adsorbent. The operations employ a plurality of tubes provided with parallel radial fins filled or covered with solid adsorbent such as Zeolite 13X located on the outside of the tubes.

The thermodynamic aspects of developing a zeolite-water adsorption refrigeration unit are well known. An article entitled, "Thermodynamic Analysis of a Solar Zeolite Refrigeration System," by S. Chang and J. A. Roux, which appeared in the Journal of Solar Energy Engineering, August 1985, Volume 107, pages 189-194 provides a discussion of the main parameters, including adsorber properties.

In adsorber/generator based cooling systems the most significant parameter is the overall heat transfer coefficient between the adsorbent bed and the cooling or heating gases per unit weight of adsorbent in the system. This parameter has been related in the literature to the cooling power per kilogram of adsorbent. The higher the cooling power, the more efficient the adsorber/generator system. Current systems are limited by requiring a high adsorbent regenerator temperature or a long cycle time to achieve relatively low cooling power values.

In a paper titled, "Application of Adsorption Cooling System to Automobiles,"by Moloyuki Suzuki, presented at the Solid Sorption Refrigeration Symposium --Paris, France, Nov. 18-20, 1992. Suzuki disclosed the results of a study to particularly point out the technological limits associated with the application of adsorption cooling systems to passenger car air conditioning. Suzuki's model considered an adsorbent bed wherein the adsorption step corresponds to the cooling step where water evaporation takes place at a water container, and wherein regeneration step corresponding to a generation step where the adsorbent bed is heated by exhaust gases to desorb the water. These steps are repeated in series requiting at least two units to achieve continuous cooling. Suzuki suggests the use of "quick cycles with a high overall heat transfer coefficient will result in acceptable designs. Currently, overall heat transfer coefficients in the ranges of 25 to 50 are reported in a paper title, "Reaction Beds for Dry Sorption Machines," by M. Groll and presented at the above mentioned Solid Sorption Refrigeration Symposium. Suzuki predicts a threshold value of 100 kW/m³ K (about 150 W/m²) for overall heat transfer k, m coefficient as a target for the future work, and further points out the need for systems with mechanical strength for use in automobiles, but does not suggest how this value which is greater than 3 times the ability of the current art can be achieved.

Prior methods of using zeolite adsorbents in devices for cooling or heating by adsorption of a refrigerating fluid on a solid adsorbent have been inefficient and difficult to prepare. Those methods of preparation included cutting natural rock into thin bricks and mounting these bricks on to heat exchange surfaces or casting powdered zeolites and mixtures thereof with clays into panels or slabs for direct contact with fluids. Methods are sought to improve the operating efficiency of these devices, and to improve the way in which the solid zeolite adsorbent is employed in these devices.

OBJECTS OF THE INVENTION

It is the object of this instant invention to provide an improved method of coating the inside of tubes.

It is a further object of the instant invention to provide an improved sorption cooling apparatus for use in waste heat recovery and air conditioning systems.

It is a further objective of the instant invention to provide an adsorbent/refrigerant system which provides a high overall efficiency within the limits of typical waste heat recovery and air conditioning cycles.

It is a still further object of the instant invention to provide a sorption cooling cycle with an improved overall thermal efficiency.

SUMMARY OF THE INVENTION

The present invention provides adsorbent composites wherein solid adsorbents are bonded to the inside surfaces of tube substrates such as aluminum metal, copper metal, aluminized steel, copperclad steel, steel, or aluminized ceramic. These composites can form linings that have improved adsorption properties over pelleted or beaded adsorbent particles as well as excellent physical and thermal cycling properties.

The present invention provides a method of lining of the inside surface of a tube with a layer of solid adsorbent selected from the group consisting of crystalline molecular sieves, activated alumina and mixtures thereof which includes the steps of heating the surface in an oxygen containing atmosphere, preferably containing at least about 1 mol % oxygen and more preferably consisting of air, to a temperature sufficient to enable bonding of the solid adsorbent to the surface and preferably oxidation of the surface, wherein the temperature is at least about 300° C., preferably between about 300° C. and 650° C. contacting the heated surface with a slurry comprising the solid adsorbent and a binder selected from the group consisting of kaolin, silica, and mixtures thereof in a suspending liquid to form a slurry-coated surface, drying the surface for a period of time ranging from about 0.25 to about 1 hour at a temperature of at least 100° C., and heating the surface to a temperature ranging from about 500° C. to about 650° C. to form an adsorbent coating on the surface. In a preferred aspect the adsorbent coated surface is heated to a temperature and for a period of time sufficient to cause hardening thereof, wherein the temperature is preferably between about 500° C. and 650° C., and the time is at least 0.25 hours and preferably about 1 hour.

The method comprising the steps of heating the surface, contacting with slurry, and drying the surface is repeated until the adsorbent layer has a uniform thickness ranging between about 0.6 to 3 mm, and preferably has a uniform thickness of from about 1.0 to 1.2 mm, before the final heating step. The composites may be used as an adsorbent layer applied to the interior surface of tubes used in devices for cooling and heating by adsorption of a refrigerant on a solid adsorbent. The crystalline molecular sieves comprise a zeolite selected from the group consisting of zeolite A, zeolite X, zeolite Y, zeolite L, chabazite, silicalite and mixtures thereof. A particular formulation was discovered which provides both strength of bonding and a more efficient method of preparing a uniform adsorbent lining for tubes. In employing adsorbent-lined tubes in sorption cooling cycles, it was discovered that zeolite Y, and more particularly zeolite Y-85, low cerium rare earth exchanged Y-84 and rare earth exchanged LZ-210 in combination with a refrigerant provided very high overall thermal efficiendes. With the above combination of the improved bonding method to provide a uniform lining of adsorbent on the inside surface of a tube; an adsorbent selected from the group consisting of zeolite Y-85, low cerium mixed rare earth exchanged Y-84, rare earth exchanged LZ-210 and mixtures thereof; and the sorbent cooling apparatus of the present invention, a significant improvement in the overall thermal efficiency with an overall heat transfer coefficient of about 175 W/m² /K in a sorption cooling cycle was achieved.

In another embodiment of the invention a zeolite-lined heat exchanger tube having a first end and a second end opposite and an inside space lined with a zeolite layer is prepared in accordance with this invention. The inside space of the tube is evacuated to a pressure of at least 1 micron of mercury while the tube is heated to a temperature of at least 350° C. The tube is maintained at these conditions for a period from about 2 hours to about 4 hours and sufficient to provide a uniform and low level of residual moisture in the zeolite layer. The zeolite layer is then brought into equilibrium with a refrigerant vapor at a level of up to about one-half the saturation value of the zeolite layer. The first end and the second end are sealed.

In a further embodiment of the invention, a desiccant cooling apparatus comprises a housing having a first fluid inlet and first fluid outlet and a second fluid inlet and fluid outlet. A plurality of zeolite-lined exchanger tubes extend substantially longitudinally within the housing. The tubes have a first end and a second end opposite and have an interior surface which is lined with a zeolite composition. The zeolite composition is bonded directly to the interior surface of the tubes and defines an internal tube space containing a refrigerant. The tubes are aligned in a parallel relationship with each other, spaced to permit transverse fluid flow and sealed at said first end. A header plate is disposed at each of the tubes. The header plates have a plurality of holes for inserting the ends of the tubes and are disposed in sealing contact with the tubes. At least one insulating baffle is disposed at a point between the ends of the tubes. The insulating baffle has a plurality of holes for inserting the tubes therethrough and is aligned generally transverse to the tubes. The insulating frame is disposed in a sealing contact with the tubes and said housing thereby defining a first zone and a second zone within said housing. The first zone is between the first end and the insulating baffle and is in fluid communication with the first fluid inlet and first fluid outlet for the flow of a first fluid therethrough. The second zone is between the insulating baffle and the second end. The second zone is in fluid communication with the second fluid inlet and the second fluid outlet for the flow of a second fluid therethrough. An end cap is disposed in sealing contact to the header plate at the second end of the tubes, thus defining a third zone in fluid communication with the interior tube space and a valve disposed on the end cap in fluid communication with the third zone.

In a still further embodiment a process for sorption cooling is provided to refrigerate a feedstream from an initial temperature to a lower temperature and comprises a series of sequential steps. A first fluid at a first temperature is passed to a first zone of a desiccant cooling apparatus containing at least one zeolite-lined tube. Each tube has a first tube portion in the first zone and a second tube portion in a second zone of the desiccant cooling apparatus. The zeolite-lined tube has a uniform lining comprising zeolite and an inner tube space containing a refrigerant. A portion of the refrigerant is desorb ed from the first tube portion to produce a vaporized refrigerant stream therein. The vaporized refrigerant stream is passed to the second tube portion. Simultaneously, a second fluid at a second temperature is passed to the second zone of the desiccant cooling apparatus to condense and reabsorb the vaporized refrigerant stream within the second tube portion. The above steps are terminated. The second fluid at the second temperature is passed to the first zone to heat the second fluid to a third temperature. Simultaneously, the feedstream at the initial temperature is passed to the second zone and the feedstream is withdrawn at the lower temperature. The passing of the second fluid and the feedstream are terminated and all of the above steps are repeated to provide a sorption cooling cycle. At least one other desiccant cooling apparatus is operated according to the sorption cooling cycle and offset by at least one-half of the sorption cooling cycle to provide continuous cooling of the feedstream. An adsorber/generator cooling system based on the present invention achieves an overall heat transfer coefficient of about 175 W/m² /K, a value which is 15 percent greater than predicted as desirable for use in automotive air conditioners.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1A is a diagrammatic illustration of a sorption cooling apparatus of the present invention for conditioning liquid streams, the housing being partially broken away to show FIG. 1B, a detail of the partition between a first and a second zone and FIG. 1C, a detail of FIG. 1B showing cross-section of a zeolite-lined tube.

FIG. 2A is a diagrammatic illustration of a sorption cooling apparatus of the present invention for conditioning vapor streams, the housing being partially broken away to show FIG. 2B, a detail of the zeolite-lined tube and the partition.

FIG. 3 is a graph of the ability of the sorbent, a low cerium rare earth exchanged zeolite Y-84 to adsorb water at various temperatures and known as an adsorption isotherm.

FIG. 4 is a graph similar to FIG. 3 for a zeolite Y-85 adsorbent.

FIG. 5 is a graph similar to FIG. 3 showing the water isotherm for a rare earth exchange zeolite IZ-210 adsorbent.

FIG. 6 is a schematic diagram of the sorption cooling apparatus of Example V.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides adsorbent-substrate composites and methods for preparing the composites by coating an inside surface of a tube with a layer of solid adsorbent, preferably molecular sieve, and more preferably zeolite. Other aspects of the present invention relate to process for utilizing the adsorbent coatings.

The substrates used in the present invention provide structural support for the solid adsorbent layer as well as provide a suitable bonding medium for the solid adsorbent and binder. The substrate may be, for example, copper, aluminum metal, steel, glass, aluminized ceramic and other similar materials. It is not necessary for the substrate to be chemically treated or washed with solvent in order to practice the present invention, however the substrate should be relatively free from large amounts of foreign matter which may adversely affect bonding, such as dirt or grease.

Virtually any synthetic or naturally occurring solid adsorbent capable of maintaining its physical integrity during the coating process is suitable for use according to the present invention. The selection of the particular solid adsorbent will depend on factors such as its effective pore diameter and the particular end use intended. The term "effective pore diameter" is conventional in the art and is used herein to functionally define the pore size in terms of the size of molecules that can enter the pores rather than actual dimensions which are often difficult to determine as the pores are often irregularly shaped, i.e., noncircular. D. W. Breck, in Zeolite Molecular Sieves, John Wiley and Sons, New York, 1974, at pages 633 to 641, provides a discussion of effective pore diameter which is hereby incorporated by reference.

Although there are a variety of solid adsorbents which are suitable for use according to the present invention including but not limited to activated carbons, activated clays, silica gel, activated alumina and crystalline molecular sieves, molecular sieves are preferred for adsorption and catalysis because of their uniform pore size, i.e., effective pore diameter. These molecular sieves include, for example, the various forms of silicoaluminophosphates, and aluminophosphates disclosed in U.S. Pat. Nos. 4,440,871, 4,310,440, and 4,567,027, hereby incorporated by reference, as well as zeolitic molecular sieves.

Zeolitic molecular sieves in the calcined form may be represented by the general formula:

    Me.sub.2/n O:Al.sub.2 O.sub.3 :xSiO.sub.2 :yH.sub.2 O

where Me is a cation, n is the valence of the cation, x has a value from about 2 to infinity and y has a value of from about 2 to 10.

Typical well known zeolites which may be used include, chabazite, also referred to as Zeolite D, clinoptilolite, erionite, faujasite, also referred to as Zeolite X and Zeolite Y, ferricrite, mordenite, Zeolite A, and Zeolite P. Detailed descriptions of the above-identified zeolites, as well as others, may be found in D. W. Breck, Zeolite Molecular Sieves, John Wiley and Sons, New York, 1974, hereby incorporated by reference. Other zeolites suitable for use according to the present invention are those having a high silica content, i.e. those having silica to alumina ratios greater than 10 and typically greater than 100. One such high silica zeolite is silicalite, as the term used herein includes both the silicapolymorph disclosed in U.S. Pat. No. 4,061,724 and also the F-silicalite disclosed in U.S. Pat. No. 4,104,294, hereby incorporated by reference.

Zeolites which are preferred for use in the present invention are those zeolites which permit the desorption of water at moderate to low temperatures and have a relatively low heat capacity. Such preferred zeolites may be selected from the group consisting of X and Y zeolites, and more particularly are selected from the group consisting of zeolite Y-85, low cerium exchanged zeolite Y-84 and rare earth exchanged IZ-210. Zeolite Y-85 is a stream stabilized modified zeolite Y the preparation of which is disclosed in U.S. Pat. No. 5,208,197 in column 7, line 16 to column 8 line 40 and is herein incorporated by reference. The low cerium exchanged zeolite Y-84 is prepared in a manner similar to the preparation of Y-85, except that the second ammonium ion exchange is carried out in the conventional manner at a pH well above 4.0 and the resulting zeolite is subjected to a rare earth exchange by contacting the zeolite with an aqueous solution of rare earth salt in the known manner. A mixed rare earth chloride salt can be added to an aqueous slurry of the ammonium exchanged zeolite to yield a zeolite product having a rare earth content generally in the range of 3.5 to 12.0 weight percent rare earth as RE₂ O₃. The product is then water washed and calcined in dry air at a temperature of from about 55° C. to about 850° C., preferably 600° C. to about 750° C. for a period of time to reduce the unit cell dimension to less than 24.6 Angstrom and more particularly in the range of 24.4 to 24.6 Angstroms. The final low cerium exchanged zeolite Y-84 has a cerium content less than about 0.2 weight percent. Zeolite LZ-210 is defined in a U.S. Pat. No. 4,503,023 in column 12, lines 5-68. The rare earth exchanged zeolite LZ-210 may be prepared by subjecting the LZ-210 to a conventional rare earth exchange step followed by the dry air calcination step described above. U.S. Pat. No. 4,503,023 is hereby incorporated by reference.

For purposes of the present invention it is required that the solid adsorbent be agglomerated with a binder in order to ensure that the coating will have suitable physical properties. Although there are a variety of synthetic and naturally occurring binder materials available such as metal oxides, clays, silicas, aluminas, silica-aluminas, silica-zirconias, silica-thorias, silica-berylias, silica-titanias, silica-alumina- thorias, silica-aluminazirconias, mixtures of these and the like, clay type binders are preferred. Examples of clays which may be employed to agglomerate the zeolites without substantially altering the adsorptive properties of the zeolite are attapulgite, kaolin, volclay, sepiolite, halloysite, polygorskite, kaolinitc, bentonitc, montmorillonite, illite and chlorite. A kaolin binder in combination with silica is particularly preferred for practicing the present invention. The addition of a small amount of silica to the binder surprisingly permitted the bonding of the solid adsorbent to high conductivity materials such as copper and steel, as well as aluminized surfaces. The preferred amount of silica in the binder ranges from about 5 to 40 wt. % and more particularly ranges from about 20 to about 30 wt. % of the binder. It is to be understood that certain solid adsorbents, such as activated alma, can function adequately as both the adsorbent and the binder. Hence, in such a case, it is not necessary to utilize an additional binder. However, it may nonetheless be advantageous to use an additional binder, such as clay, for economic reasons, etc.

According to the present invention the substrate is coated with the solid adsorbent by contacting the surface of the substrate, after heating the surface as hereinafter described, with a slurry comprising the solid adsorbent and binder. The solid particles used in the slurry including both the solid adsorbent and binder material may be of any size to functionally suitable in the present invention. However, the solid adsorbent and binder are desirably present as small particles, preferably having a particle size of from about 1 to 500 microns more preferably from about 1 to 50 microns.

If necessary, the solid particles may be subjected to mechanical size reduction, e.g., grinding, crushing, milling and the like, in order to obtain the desired particle size. However, it is preferred that the solid particles be more smooth, and more preferably also more spherical, relative to solid particles of similar composition obtained by mechanical size reduction. Such particle smoothness and sphericity tends to improve evenness of the mating and may also allow increased solids loading in the slurry, if desired. One particularly useful processing step to achieve such smoothness and sphericity is to employ spray drying as part of the said particle manufacturing process to form the solid particles or precursors of the solid particles. An additional advantage of employing such spray drying is that the conditions of such step can be controlled so that the product solid particles are of a desired particle size or size range. The use of spray drying in such solid particle manufacturing is conventional and well known, and therefore need not be discussed in detail here. It is to be understood that the solid adsorbent and binder may be agglomerated and subjected to size reduction prior to forming the slurry, if desired.

The solid adsorbent and binder may be mixed in the slurry in a variety of proportions, whether as segregated or agglomerated particles, although it-is generally desirable to use only as much binder as is required to give sufficient strength to the coated surface. It is preferred that the adsorbent portion comprises about 60 to 95 wt. % of the total weight of solids, i.e., adsorbent and binder, in the slurry and that the remaining 5 to 40 wt. % comprises binder. In addition to the adsorbent and binder, the slurry may contain a dispersing agent or surfactant to aid in suspending the particles or vary the viscosity of the slurry. Suitable surfactants include for example, Dispex, a salt of a polymedc carboxylic acid available from Allied Colloids, Suffolk, Va., and TSPP, a tetrasodium pyrophosphate available from Monsanto, St. Louis, Mo. When a surfactant or dispersing agent is used, it is preferred that its concentration be in the range of about 0.5 to 5.0 wt. % of the solids content of the slurry.

While it can be appreciated that the solid adsorbent and binder can be suspended in a dry slurry, i.e., fluidized bed, it is desirable in accordance with the present invention that the slurry contain a suspending liquid. The suspending liquid should be one which is not likely to chemically react, e.g., by itself or with the substrate or other components in the slurry. More preferably, the suspending liquid should be substantially non-reactive and should not interfere with the internal pores of the solid adsorbent. Water is a preferred suspending liquid for use according to the present invention. The proportion of suspending liquid can be varied to adjust the viscosity of the slurry and hence, the thickness of the coating. The determination of the appropriate proportions to achieve the desired coating thickness can be made experimentally by measuring the thickness resulting from a given slurry and then either increasing the solids proportion, i.e. higher viscosity, to obtain a thicker coating, or decreasing the solids proportion, i.e., lower viscosity, to obtain a thinner coating. One way to determine the thickness of the coating is to calculate the area density coverage, i.e., the weight of solid adsorbent per unit area, and then divide by the density of the solid adsorbent. It is generally preferred that the solid materials comprise about 10 to 40 wt. %, and preferably about 20 to 40 wt. % of the total weight of the slurry, and more preferably about 25 to about 35 wt. % of the slurry with the balance preferably consisting essentially of the suspending liquid and any surfactants or dispersing agents.

In order to ensure sufficient bonding of the solid adsorbent to the substrate, it is necessary to heat the surface of the substrate in an oxygen containing atmosphere, preferably containing at least about 1 mol% oxygen and more preferably consisting of air, to a temperature of at least 300° C., preferably between about 300°-650° C. This heating preferably causes the surface of the substrate to become oxidized. While not wishing to be bound to any particular theory, it is suspected that the oxidation is at least partially responsible for achieving sufficient bonding.

The heated surface is then contacted with the slurry, preferably by dipping the surface into the slurry or by spraying the slurry onto the surface, to form a slurry-coated surface. In the case of coating the inside surface of a tube, it was found that heating the tube, stoppering one end of the tube, filling the tube with slurry and draining the tube after a period of time ranging from about 0.25 to 2 min., and preferably from about 0.5 to 1 min. provided an efficient method of uniformly coating the surface. If, after the initial contacting, it is desired to increase the thickness of the coating, additional contacting steps can be performed. When such additional contacting is performed, it is necessary to permit the coating to dry preferably in an oxygen containing atmosphere at a temperature of at least 100° C. for a period of at least 0.1 hours to preferably about 1 hour. It is preferred to preheat the coated surface to a temperature of about 300° C. before additionally contacting the surface with the slurry.

When the desired coating thickness has been obtained, the adsorbent coated surface is heated to a temperature and for a period of time sufficient to cause hardening of the coated surface. This temperature should be at least about 200° C., preferably between about 400° C. and 650° C., and most preferably between about 550°-650° C. The time required to cause hardening of the coated surface is desirably at least 0.1 hours and less than about 1 hour.

The resulting adsorbent-substrate composite comprises an underlying metallic layer and another layer bonded to the surface of the metallic substrate consisting essentially of adsorbent and binder. These coatings provide a high surface area as well as a minimum diffusion path for the components adsorbed on the adsorbent and hence, superior rates of adsorption compared to pelleted or beaded forms of adsorbent. Moreover, the adsorbent coatings have excellent physical durability and are resistant to chipping and flaking. Furthermore, despite differences in the thermal expansion properties between the adsorbent and the metallic substrate, the adsorbent coatings of the present invention advantageously retain their physical integrity even after repeated thermal cycling. In addition, when the present invention is employed in heat transfer equipment, and the adsorbent layer has a uniform thickness ranging from 0.6 to 3.0 mm, and preferably ranging from 1.0 to 1.2 mm, the adsorbent coating provides an acceptably small thermal resistance. Without wishing to be bound to any particular theory, it is thought that the heating step performed prior to the contacting step, in addition to causing oxidation of the substrate, may change the grain structure of the substrate to advantageously provide improved bonding properties.

In accordance with the present invention, adsorbents such as natural zeolites, synthetic zeolites, binders, and mixtures thereof may be applied to the inside surfaces of tubes for use in devices for cooling and heating by adsorption of a refrigerating fluid on a solid adsorbent. The preferred tubes are thin-walled and may have a plurality of fins disposed on the outside surface of the tubes. The inside surface of the tube is coated with a thin layer of solid adsorbent between about 0.1 and less than 3 mm thick. Preferably, the layer of solid adsorbent, such as zeolite, has a uniform thickness of between about 0.6 and about 1.6 mm, and most preferably, the uniform thickness of the solid adsorbent layer is between about 1.0 and 1.2 mm. The coated tubes are typically evacuated to a high vacuum of at least 1 micron of mercury at a temperature of at least 350° C. for a period of at least about 2 to 4 hours, filled with a refrigerant, such as water, propane, butane, ammonia, CO₂, SO₂ , sulfur hexafluoride, Refrigerant 11, Refrigerant 12, Refrigerant 21, and Refrigerant 22, light alcohols and mixtures thereof, and sealed in a closed system by either sealing both ends of the tube or by providing a closed refrigerant circuit comprising a reservoir, an evaporator, and a condenser.

Particularly with respect to FIG. 1A of the drawings, one embodiment of the desiccant cooling apparatus of the present invention is indicated generally at 10. The desiccant cooling apparatus 10 comprises a housing 16 having a first fluid inlet 14 and a first fluid outlet 18 and a second fluid inlet 20 and a second fluid outlet 22 and an interior 11. A plurality of zeolite-lined exchanger tubes 24 extend longitudinally within the interior of the housing. The tubes are aligned with each other and spaced to permit transverse fluid flow. Header plates 12 and 28 are disposed on each end of the tubes. A partition 40 divides the interior of the housing into a first zone and a second zone. The first zone is in fluid communication with the first fluid inlet and first fluid outlet for the flow of a first fluid therethrough. The second zone is in fluid communication with the second inlet and the second outlet to permit the flow of a second fluid therethrough. End cap 32 is disposed at the ends of the housing in sealing contact with the header plates defining a third zone which is in fluid communication with the interior space of the tubes. A valve 34, disposed on the end cap is in fluid communication with the third zone.

Referring to FIG. 1B which is a detail of FIG. 1A, a partition 40 is shown at a point between the ends of the tubes. The partition and the header plates have a plurality of holes 42 for inserting the tubes therethrough and are aligned generally transverse to the tubes. The header plates 12, 28 and the partition 10 are disposed in sealing contact with the tubes.

Referring to FIG. 1C which is a detail of FIG. 1B, a view of a zeolite-lined tube is shown. A zeolite composition 52 is slip-coated, or bonded directly to the inside surface 50 of the zeolite-lined tube. The zeolite-lined tube has an interior space 53 containing a refrigerant. A sealing means 43 disposes the tubes in sealing contact with the header plates and the partition prevents fluid flow beyond the header plates or the partition. A second sealing means 45 disposed on the partition prevents fluid flow from one side of the partition to another.

With respect to FIG. 2, another embodiment of the desiccant cooling apparatus is shown at 70. The desiccant cooling apparatus is configured in a manner as described with respect to FIG. 1 with the overall shape of the apparatus arranged to permit vapor or gas flow through the first and second zones. Similar elements between FIGS. 1A, 1B, 1C and FIGS. 2A and 2B are shown with the same numbers. Fins 54 are shown disposed on the tubes in FIG. 2B.

The zeolite coated heat exchanger tube may be employed in a heat pump or refrigeration cycle which operates between a hot fluid temperature and a cold fluid temperature. The solid adsorbent and refrigerant combination is selected according to those boundary conditions of the heat pump or refrigeration cycle, so that at least a portion of the refrigerant will be desorbed from the solid adsorbent at the hot fluid temperature and at least a portion of the refrigerant will be adsorbed at the cold fluid temperature. Preferably, the hot fluid temperature selected for the operation of the process will be relatively constant and range from about 80° C. to about 250° C. In the practice of the invention, the hot fluid may be an exhaust gas from any industrial process or an internal combustion engine. Generally, any fluid or gas stream at ambient conditions can be employed as the cold fluid. Preferably, the cold fluid temperature will be less than the hot fluid temperature and range from about 20° C. to about 50° C. Preferably, the lower desired temperature to which the feedstream is to be cooled will range from about 20° C. to about 0° C.

The process of the invention to refrigerate a feedstream from an available temperature to a lower desired temperature will comprise a series of sequential steps. A first fluid at a hot fluid temperature is passed to a first zone of a desiccant cooling apparatus containing at least one zeolite-lined tube. The zeolite-lined tube has a first portion in the first zone and a second portion in a second zone of the desiccant cooling apparatus. The zeolite tube is prepared in the manner of the present invention and has a uniform lining of an adsorbent. The zeolite-lined tube has an inner space containing a refrigerant. The passing of the hot, first fluid on the outside of the zeolite-lined tube causes the refrigerant adsorbed thereon to be desorbed to produce a vaporized refrigerant stream. The vaporized refrigerant stream is passed to the second tube portion. Simultaneously, a second fluid at a second temperature, preferably at the cold fluid temperature is passed to the second zone of the desiccant cooling apparatus. In the second zone, the second fluid contacts the outside of the zeolite-lined tube, cooling the second portion of the zeolite-lined tube and resulting in the condensation and readsorption of at least a portion of the refrigerant within the second portion of the zeolite-lined tube. These simultaneous steps are terminated at a point midway in the cycle. At this point the flows are switched such that the second cold fluid is passed to the first zone to heat the second fluid, thus removing heat from the first zone. Simultaneously, the feedstream to be cooled is passed to the second zone and the feedstream at the lower desired temperature is withdrawn. These later steps are terminated after a period of time and the cycle is complete. To provide continuous cooling, at least one other desiccant cooling apparatus may be operated with a cycle which is offset from the above cycle by at least one-half of the cycle. In an automobile, the at least one other desiccant cooling apparatus may be insulated from the first desiccant cooling apparatus and be contained within a common housing. In practice, the second fluid may be a portion of the feedstream which may be ambient air or a process stream comprising light hydrocarbons or air. Furthermore, it is within the scope of the present invention to separate the adsorption and generation sections of the process whereby the first zone contacting the first tube portion and the second tube portion are physically separated and refrigerant flows thereinbetween through any number of conduits and heat exchangers.:

Furthermore, each solid adsorbent and refrigerant combination will have a saturation value which refers to the equilibrium amount of refrigerant which will be adsorbed by the solid adsorbent as the vapor pressure in equilibrium with the adsorbent approaches the saturation vapor pressure of the refrigerant at the adsorbent temperature. For example, a Zeolite 13X-water system has a saturation value from about 20% to about 28% weight of the zeolite. For the operation of the zeolite-lined heat exchanger tube, the tube is filled up to about 50% of the saturation value to permit at least half of the tube to operate in the hot fluid region and the remaining portion to operate in the cold fluid region. In this manner, desorption will take place at the hot fluid, or first end of the tube while adsorption and any condensation will take place at the cold fluid, or second end of the tube. Thus, for the Zeolite 13X-water system, about 50% of the saturation value of the zeolite layer is from about 10% to about 14% weight of the zeolite layer.

Therefore, in the process of preparing a zeolite coated heat exchanger tube, following the activation of the zeolite layer by heating and evacuation for a sufficient time, the tube is cooled to an appropriate temperature and brought into equilibrium at an appropriate pressure with a refrigerant vapor such that the level of refrigerant vapor in the tube is up to about one-half the saturation value of the zeolite layer. At this point the tube is sealed at the first and second ends, or the system is closed.

The outside surfaces of the tubes may be provided with fins or similar devices to facilitate the heat transfer between the shell side fluids and the refrigerant. Preferably, the tubes will be thin-walled and constructed of aluminum or similar high heat conductivity material with a low mass. Preferred high heat conductivity materials include aluminum, copper, steel, ceramics, glass, aluminized steels, and alloys thereof.

EXAMPLES

The following examples are provided for illustrative purposes and are not intended to limit the scope of the claims that follow.

EXAMPLE I

A low cerium rare earth exchanged Y-84 was prepared from zeolite Y-84. Y-84 is the ammonium form of stabilized Y zeolite with an A_(o) of 24.55 Angstroms, an NH₄ /Al of 0.3 and a Na/Al of less than 0.1. The Y-84 was obtained from UOP in Des Plaines, Ill. The Y-84 was subject to a rare earth chloride exchange with a mixed rare earth chloride salt coning 24.5 wt. % Lanthanium and 0.8 wt. % cerium. The material was water washed at a rate of 6 pounds of hot water per pound of Y-84. The product was subjected to calcining in dry air at a temperature of about 650° C. The resulting product had an A_(o) of 24.51, a rare earth loading of about 5.5 wt. %, a Si/Al₂ O₃ ratio of 5.2, an oxygen capacity of 28.1, a water capacity of 24.08 and a cerium content of less than 0.2 wt. % on a dry basis.

EXAMPLE II

The inside surface of a 12 inch length of copper tube, 3/4" in diameter, was lined with the low cerium rare earth exchanged Y-84 adsorbent. Example I, according to the coating method of the present invention. The inside surface tube was sand blasted to clean the surface. The tube was heated to a temperature of about 300° C. in an oxygen containing atmosphere and one end of the tube was stoppered. A slurry with the following composition: 80% Adsorbent, 15% Kaolin and 5% Silica was poured into the tube. After about 1 minute, the stopper was removed and the slurry permitted to flow out of the tube. The solids content of the slurry was about 35 wt. % in water, the suspending liquid. No dispersion agent was added. It was found that the addition of the silica (SiO₂) to the binder was critical to obtaining a uniform bonding of the adsorbent to the inside surface of the copper tube. The coated tube was then dried in air at about 100° C. for about 1 hour. Following the drying step, the tube was preheated to a temperature of about 300° C., stoppered and refilled with slurry for about 1 minute. This procedure was repeated 4 times to obtain a uniform coating of adsorbent with a thickness of about 1.0 to 1.2 mm on the inside of the tube. On removing the slurry from the tube after the final coating, the tube was heated at about 550° C. for a period of about one hour to calcine the adsorbent and harden the adsorbent coating. It was found that preheating the tube between slurry applications improved the bonding. However, it was discovered that heating the clay above 500° C. between applications could convert the Kaolin to a metaKaolin structure which would prevent further application.

EXAMPLE III

A 12 inch length of a tube with an inside copper substrate was lined with zeolite Y-85 by following the method of the present invention and the procedure of Example II.

EXAMPLE IV

A modified BET adsorption apparatus to measure the volumetric adsorption of an adsorbent was employed to produce an adsorption isotherm for the adsorbent coated tube. Temperature and pressure measurements in a vessel of known volume were made and a weight loading was calculated. The results were plotted as a function of pressure over a range from 10⁻⁶ tort to about 1 atmosphere. FIG. 3 presents the adsorption isotherms for the low cerium rare earth exchanged zeolite Y-84 and water developed at 25°, 50°, and 80° C. FIG. 4 presents adsorption isotherms for zeolite Y-85 and water at 25°, 50°, and 80° C. FIG. 5 presents the adsorption isotherms for a rare earth exchanged LZ-210 and water at 25° and 80° C. A comparison of the delta loadings between 80° C. and 25° C. at a pressure of 0.5 kPa for these three adsorbents is shown in the Table 1 below:

                  TABLE 1                                                          ______________________________________                                         DELTA LOADING WT % AT PRESSURE OF 0.5 kPa                                      ADSORBENT @ 80° C.                                                                          @ 25° C.                                                                         Δ LOADING, WT %                             ______________________________________                                         Y-85      4         20       16                                                CRE-84    3         19       16                                                RE-LZ210  4         20       16                                                ______________________________________                                    

The above adsorbents exhibit a similar tendency for the adsorption of water at ambient conditions and the desorption of water at the relatively low temperature of 80° C. with delta loadings of about 16 wt % between 25° C. and 80° C.

EXAMPLE V

The zeolite-lined tubes of Example II and Example III were used to construct two single tube, tube in shell, heat exchangers by enclosing the outside of the zeolite-lined tubes in separate steel jackets, each jacket having a fluid inlet and a fluid outlet. The zeolite-lined tubes, 110 and 120, were assembled as shown in FIG. 6 to operate in a sorption cooling process with water as the refrigerant. The major components of the process were the condensing heat exchanger 130, the condenser receiver 140, the evaporating heat exchanger 160 and the refrigerant reservoir 150. The condenser receiver was a 10 ml vial and the refrigerant reservoir was a calibrated vessel with a 50 ml capacity. The flow of water to the evaporating heat exchanger 160 was controlled by needle valve 170. The first zeolite-lined tube 110 was connected to the condensing heat exchanger 130 by line 111 valve 112 and lines 113 and 114. Similarly, the second zeolite-lined tube was connected to the condensing heat exchanger by line 116, valve 115 and lines 113 and 114. The first zeolite-lined tube is connected to the evaporating heat exchanger 160 by line 123, valve 122 and lines 121 and 119. The second zeolite-lined tube 120 by line 117, valve 118 and lines 121 and 119.

During the experiments, a heated fluid was supplied to one zeolite-lined tube while supplying ambient temperature fluid to the other tube. Ambient temperature fluid was continuously supplied to both the condensing heat exchanger and the evaporating heat exchanger. The experiments were begun with a full evaporator reservoir and an empty condenser receiver. One tube was activated at a regeneration temperature of about 80° C. while the other was brought to near a saturated state by exposure to the evaporator reservoir. The entire system was evacuated so that the total pressure of the system was in equilibrium with the adsorbent loading at ambient temperature. This value is approximately equal to the vapor pressure of water at the ambient temperature.

The experimental cycle was begun by applying heated fluid at a per selected regeneration or desorption temperature to the saturated tube, putting it in generation mode, while the activated tube was maintained at ambient temperature by cooling stream, putting this tube in the adsorber mode. After one-half the cycle time had elapsed, the heating and cooling streams and the valve settings were switched so that the tube which was in the generation mode was now in fluid communication with the evaporator, and the tube which was in the adsorber mode was put in fluid communication with the condenser and an amount of condensable was collected in the condenser receiver. The remainder of the cycle was carried out and the procedure was repeated until the receiver was full.

The tubes were cycled between heating mode and cooling mode in a cycle that required a total time of about 6 minutes, equally divided between heating and cooling. The results of the experiments are summarized in Table 2. Each entry in Table 2 represents a separate run at increasing regeneration temperatures ranging from 65° C. to 96° C. below:

                                      TABLE 2                                      __________________________________________________________________________     Ave. Amt. of                                                                             Ave. Water                                                                             Regen       Cooling                                          Water     Loading/Cycle/                                                                         Temp, °C.                                                                     Evap  Capacity                                         Condensed ml                                                                             Tube wt %                                                                              (Ave) Temp, °C.                                                                     BTU/Hr/Ft.sup.3                                  __________________________________________________________________________     A 0.5     3.6     65    17.5  3761                                             B 0.63    4.5     70    16.5  4751                                             C 0.73    5.2     76.7  16.5  5496                                             D 0.76    5.4     80.7  14.5  5733                                             E 0.76    5.4     85.5  16.5  5737                                             F 0.78    5.4     85.5  15.8  5899                                             G 0.85    6.1     89.6  15.5  6406                                             __________________________________________________________________________

The cooling capacity was derived from the amount of condensate adsorbed and the heat of vaporization of the refrigerant, water. The measured cooling capacities for the zeolite-line tubes of the instant invention were at least twice that reported in the literature. The average overall heat transfer coefficient for the zeolite-lined tubes was approximately 175 W/m² /K. 

We claim:
 1. A method of lining an inside surface of a tube with a layer of solid adsorbent selected from the group of crystalline molecular sieves, activated alumina and mixtures thereof which comprises:a) heating said surface in an oxygen containing atmosphere to a temperature of at least 300° C. and sufficient to enable bonding of the solid adsorbent to said surface; b) contacting said surface with a slurry comprising the solid adsorbent and a binder comprising kaolin, silica and mixtures thereof in a suspending liquid to form a slurry-coated surface; c) drying said surface for a period ranging from about 0.1 hour to about 1 hour at a temperature of about 100° C.; and d) heating said surface to a temperature ranging from about 500° C. to about 650° C. to form an adsorbent lining on said surface.
 2. The method of claim 1 further comprising repeating steps (a) through (c) until said adsorbent lining has reached a uniform thickness of between about 0.6 mm and about 3.0 mm., before step (d).
 3. The method of claim 1 wherein said crystalline molecular sieves comprise a zeolite selected from the group consisting of zeolite A, zeolite X, zeolite Y, zeolite L, chabazite, silicalite and mixtures thereof.
 4. The method of claim 3 wherein said zeolite is selected from the group consisting of zeolite Y and zeolite L.
 5. The method of claim 4 wherein the zeolite comprises zeolite Y-85.
 6. The method of claim 4 wherein the zeolite comprises a low cerium mixed rare earth exchanged zeolite Y-84.
 7. The method of claim 4 wherein the zeolite comprises a rare earth exchanged zeolite LZ-210.
 8. The method of claim 1 wherein said slurry comprises from about 10% to about 20% kaolin.
 9. The method of claim 1 wherein said slurry comprises from about 1% to about 10% silica,
 10. The method of claim 8 wherein said slurry has a solids content which ranges from about 20% to about 40%
 11. The method of claim 10 wherein said solids content ranges from about 25% to about 35%.
 12. The method of claim 1 wherein said tube is selected from the group consisting of aluminum, copper, glass, ceramics, steels, alloys and composites thereof.
 13. The method of claim 12 wherein said tube comprises aluminum.
 14. The method of claim 12 wherein said tube comprises copper. 